TW201839041A - Photosensitive resin composition and cured product thereof - Google Patents

Abstract

The present invention is a negative-acting photosensitive resin composition including (A) a compound having a triazine ring and represented by formula (1) (in formula (1), each R1 independently represents an organic group, wherein at least one R1 represents an organic group having a glycidyl group or an organic group having an oxetanyl group), (B) an epoxy resin having in each molecule a benzene skeleton and at least two epoxy groups and having an epoxy equivalent weight of not more than 500 g/eq., and (C) a cationic photopolymerization initiator. The content of the (A) compound represented by formula (1) with reference to the (B) epoxy resin is 1 to 50 mass%. The (B) epoxy resin satisfies at least one of the following conditions (i) and (ii): condition (i) a weight-average molecular weight of at least 500, and condition (ii) a softening point of at least 40 DEG C.

Description

Photosensitive resin composition and cured product thereof

The invention relates to a MEMS (microelectromechanical system) part, micromechanical part, microfluidic part, μ-TAS (micro-total analysis system) part, inkjet printer part, microreactor part, conductive layer, Production of LIGA parts, micro injection molding, stampers and stamps suitable for hot embossing, spacers or stencils suitable for micro printing applications, MEMS package parts, semiconductor package parts, BioMEMS and biophotonic components and printed wiring boards (PWB) The negative-type photosensitive resin composition has a good resolution. The present invention further relates to a cured product of the negative photosensitive resin composition, which has a high elastic modulus at high temperatures and good adhesion to various substrates.

Recently, photoresistable resists are widely used in semiconductor and MEMS and micromechanical applications. In this application, photolithography is achieved by selectively removing exposed or non-exposed areas by developing with a developer while patterning exposure on the substrate. The resist (photoresist) that can be lithographically processed has a positive type or a negative type, and those in which the exposed portion is dissolved in the developer are positive, and similarly, those that are insoluble are negative. With top-level electronic packaging applications and MEMS applications, not only can it form a uniform spin coating layer, but it also requires a high aspect ratio, a straight sidewall shape in a thick film, and high adhesion to the substrate. Here, the aspect ratio is calculated from a resist film thickness / pattern line width, and represents an important characteristic of photolithographic performance.

As such a photoresist, a polycationic bisphenol A phenolic epoxy resin (trade name: EPON SU-8 resin, manufactured by Resolution Performance Products) and a photocationic polymerization reaction start such as CYRACURE UVI-6974 manufactured by Dow Chemical are included. A negative chemically amplified photoresist composition containing an initiator (the photocationic polymerization initiator is composed of an aromatic hexafluoroantimonate propylene carbonate solution) is widely known. Since the photoresist composition has a very low light absorption in a wavelength range of 350 to 450 nm, it is widely known as a photoresist composition capable of performing thick film photolithography. This photoresist composition is applied to various substrates by a method such as spin coating or curtain coating, and the solvent is volatilized by baking to form a solid photoresist layer having a thickness of 100 μm or more. Furthermore, the solid photoresist layer can be irradiated with near-ultraviolet rays through various exposure methods such as contact exposure, proximity exposure, or projection exposure, and photolithography can be performed. Next, by immersing it in a developing solution and dissolving the non-exposed areas, a negative image of a high-resolution photomask can be formed on the substrate.

When the hardened material of the photoresist is used as a component such as a semiconductor package, for example, when the step of resin-sealing the hardened material of the photoresist with other components is included in the manufacture of a semiconductor package, the hardening It is required to maintain a high modulus of elasticity at a high temperature when the resin is encapsulated.

Furthermore, in recent years, not only silicon wafers that have been commonly used before but also various substrates such as silicon nitride and lithium tantalate are used in substrates for MEMS components, MEMS packages, and semiconductor packages. Therefore, the photoresist also requires good adhesion of the cured product to these substrates.

Patent Document 1 discloses a photosensitive resin composition containing a photocationic polymerization initiator of a specific structure and a polyfunctional epoxy resin. In the example of this document, it is described that the hardened | cured material of this photosensitive resin composition has favorable adhesiveness with respect to a silicon wafer. However, in this document, there is no mention of any elastic modulus at high temperatures and adhesion to substrates other than silicon wafers. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Re-publication Patent WO2012 / 008472

[Problems to be Solved by the Invention] The present invention has been made in view of the problems described above, and an object thereof is to provide a negative photosensitive resin composition having a good resolution and a cured product. It also maintains a high elastic modulus at high temperatures and has good adhesion to various substrates other than silicon wafers. [Technical means to solve the problem]

As a result of intensive review by the inventors, it was found that a compound containing a triazahexacyclic structure with a specific structure, a polyfunctional epoxy resin having a benzene structure and meeting specific parameters, and a negative type of a photocationic polymerization initiator The photosensitive resin composition can solve the above-mentioned problems and complete the present invention.

The present invention relates to the following aspects. [1] A negative-type photosensitive resin composition containing: (A) a compound having the following formula (1): [Chemical Formula 1] (In the formula (1), R ₁ each independently represents an organic group. However, at least one of R ₁ represents an organic group having an epoxy group or an organic group having an oxetanyl group.) A cyclic compound, (B) an epoxy resin having an epoxy equivalent of 500 g / eq. Or less with a benzene structure and two or more epoxy groups in one molecule, and (C) a photocationic polymerization initiator, wherein The content of the compound represented by the formula (A) in the formula (1) is 1 to 50% by mass with respect to the (B) epoxy resin, and the condition (i) that the (B) epoxy resin satisfies a weight average molecular weight of 500 or more And at least one of the conditions (i) where the softening point is 40 ° C or higher. [2] The negative photosensitive resin composition according to the above item [1], wherein at least one of R ₁ is represented by the following formula (1-1): [Chemical Formula 2] (In the formula (1-1), R ₂ represents an alkylene group having 1 to 8 carbon atoms.) The following formula (1-2) [Chemical formula 3] (In the formula (1-2), R ₃ represents an alkylene group having 1 to 8 carbon atoms, and R ₄ represents an alkyl group having 1 to 6 carbon atoms.) Or the following formula (1-3) [Chemical Formula 4] Represents an organic group. [3] The negative photosensitive resin composition described in the above item [2], wherein any one of R ₁ is an organic group represented by the formula (1-1) and an organic group represented by the formula (1-2) Or an organic group represented by formula (1-3). [4] The negative photosensitive resin composition according to the above item [2], wherein at least one of R ₁ is represented by the following formula (1-4): [Chemical Formula 5] (In the formula (1-4), R ₅ represents a hydrogen atom or a methyl group.) An organic group represented by R ₅ . [5]. The negative photosensitive resin composition according to any one of the above [1] to [4], wherein (B) the epoxy equivalent of a benzene structure and two or more epoxy groups in one molecule is 500 g / eq. The following epoxy resin is selected from the following formula (2): [Chemical Formula 6] (In formula (2), R each independently represents an epoxy group or a hydrogen atom, and at least two of the plurality of R are an epoxy group. K represents an average value, and is a real number in a range of 0 to 30.) The epoxy resin (B-1) represented by the following formula (3) [Chemical formula 7] (In formula (3), R ₆ , R _7, and R ₈ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. P represents an average value and a real number in a range of 1 to 30.) The epoxy resin (B-2) is represented by the following formula (4) [Chemical formula 8] (In formula (4), n and m represent average values, n is a real number in the range of 1 to 30, m is a real number in the range of 0.1 to 30, and R ₉ and R ₁₀ each independently represent the number of hydrogen atoms and carbon atoms. It is an 1-4 alkyl group or a trifluoromethyl group. The epoxy resin (B-3) represented by the following formula (5) [Chemical formula 9] (In the formula (5), q represents an average value, and is a real number in a range of 1 to 30.) The epoxy resin (B-4) represented by the following formula (6) [Chemical formula 10] The reactant of the phenol derivative and epihalohydrin is epoxy resin (B-5). By using an epoxy compound having at least two epoxy groups in one molecule and at least one epoxy group in one molecule, The epoxy resin (B-6) obtained by reacting a reactant of a compound having one or more hydroxyl groups and one carboxyl group with polyprotic anhydride is represented by the following formula (7): [Chemical formula 11] (In the formula (7), s represents an average value, and is a real number in a range of 1 to 10.) The epoxy resin (B-7) represented by the formula (8) is represented by the following formula (8) [Chemical formula 12] (In the formula (8), t represents an average value, and is a real number in a range of 0.1 to 5.) The epoxy resin (B-8) represented by the formula (9) and the following formula (9) [Chemical formula 13] (In formula (9), r represents an average value, and is a real number in a range of 0.1 to 6.) One or two or more groups of the epoxy resin (B-9) group represented by the formula (9). [6]. A dry film resist comprising the negative photosensitive resin composition according to any one of the items [1] to [5]. [7]. A negative photosensitive resin composition according to any one of the above [1] to [5] or a cured product of the dry film resist according to the above [6]. [8]. A wafer level package (WAFER LEVEL PACKAGE), which includes the hardened product described in [7] above. [9]. An adhesive layer is an adhesive layer between a substrate and an adherend, and includes a hardened body as described in [7] above. [Inventive effect]

The negative photosensitive resin composition of the present invention has a good resolution and a high effect in controlling the generation of residues after development. The cured product also maintains a high elastic modulus at high temperatures. Various substrates have good adhesion. Therefore, the negative photosensitive resin composition can be preferably used for MEMS parts, micromechanical parts, and semiconductor packaging parts.

Hereinafter, the present invention will be described. The negative-type photosensitive resin composition of the present invention contains (A) a compound having a triazine ring represented by the formula (1) (hereinafter, simply referred to as "(A) component"). In Formula (1), R ₁ each independently represents an organic group. The organic group represented by R ₁ in formula (1) is not particularly limited as long as it does not impede the characteristics required for the resin composition. For example, functional groups such as hydroxyl, aldehyde, carboxyl, nitro, amine, sulfonic, and nitrile groups, halogen groups such as bromine atom, chlorine atom, fluorine atom, and iodine atom, and aliphatic groups which may be substituted by these groups. Residues excluding a hydrogen atom from a hydrocarbon, an aromatic hydrocarbon, or a heterocyclic compound are also included in the category of the organic group represented by R ₁ in formula (1). However, at least one of R ₁ in the formula (1) represents an organic group having an epoxy group or an organic group having an oxetanyl group. That is, the compound having a triazacyclo ring represented by the formula (1) is a compound having at least one epoxy group or oxetanyl group. The organic group having a glycidyl group or an oxetanyl group represented by R ₁ in formula (1) is not particularly limited as long as it has a glycidyl group or an oxetanyl group. An organic group represented by the formula (1-1), (1-2), or (1-3).

In the formula (1-1), R ₂ represents an alkylene group having 1 to 8 carbon atoms. The alkylene group having 1 to 8 carbon atoms represented by R ₂ in formula (1-1) is not limited to any of linear, branched, or cyclic as long as the carbon number is 1 to 8 . The alkylene group represented by R ₂ may have an alkyl group as a substituent. When the alkyl group is used as a substituent, the total number of carbon atoms of the alkylene group and the number of carbon atoms of the alkyl group may be 1 to 8. The number of carbon atoms in the main chain of the alkylene group represented by formula (1-1) is preferably 1 to 6. Specific examples of the olefin having 1 to 6 carbon atoms include methylene, vinyl, n-propenyl, n-butenyl, n-pentenyl, n-hexenyl, iso Propylene, isobutenyl, isopentenyl, neopentenyl, isohexenyl, cyclohexyl and the like. From the viewpoints of lithography, adhesion, and heat resistance of the obtained hardened material, a methylene group, a vinyl group, or an n-propylene group is preferable, and an n-propylene group is more preferable.

In the formula (1-2), R ₃ represents an alkylene group having 1 to 8 carbon atoms, and R ₄ represents an alkyl group having 1 to 6 carbon atoms. As the alkylene group having 1 to 8 carbon atoms represented by R ₃ in formula (1-2), an alkylene group having 1 to 8 carbon atoms represented by R ₂ in formula (1-1) can be listed. Those having the same alkyl group can also be exemplified. The alkyl group having 1 to 6 carbon atoms represented by R ₄ in formula (1-2) is not limited to any one of linear, branched, or cyclic as long as the carbon number is 1 to 6. Examples of the alkyl group having 1 to 6 carbon atoms represented by R ₄ in formula (1-2) include a linear or branched alkyl group having 1 to 6 carbon atoms and a carbon number of 5 Or 6 cyclic alkyl (cyclopentyl and cyclohexyl). R _{4 is} preferably a linear or branched alkyl group having 1 to 6 carbon atoms. R _{4 is more} preferably a linear alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably an ethyl group.

As the component (A), it is also preferable to use an organic group represented by the formula (1-1), (1-2), or (1-3) in R ₁ and the formula (1- 4) A compound represented by an organic group. In the formula (1-4), R ₅ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

As (A) component, the compound represented by preferable formula (1) is described below. (Ⅰ) R ₁ of all, an organic group of compounds represented by the formula n- propenyl group (1-1) R ₂ is. (Ⅱ) R ₁ of all, R ₂ the methylene group of the organic compound in the formula (1-1) is represented. (Ⅲ) R ₁ of all, R ₃ is a methylene group of an ethyl group and R ₄ is an organic group of a compound of formula (1-2). (Ii) All of R ₁ are compounds of an organic group represented by formula (1-3). (I) One of R ₁ is an organic group represented by formula (1-1), R ₂ is a methylene group, the remaining two of R ₁ are, and R ₅ is a hydrogen atom, represented by formula (1-4) Organic compounds. (Ⅵ) R ₁ is of the two, R ₂ is a methylene group of the organic group represented by the formula (1-1), the remaining one of R _1, R ₅ is represented by the formula (1-4) a hydrogen atoms Organic compounds.

The (A) component can be obtained as a commercial item. Specific examples thereof include TEPIC (the above (ⅱ)), TEPIC-VL (the above (ⅰ)), TEPIC-PAS (a mixture of the modifiers of the above (ⅱ) and (ⅱ)), TEPIC-G , TEPIC-S, TEPIC-SP, TEPIC-SS, TEPIC-HP, TEPIC-L, TEPIC-FL, and TEPIC-UC (above (ⅴ)) TEPIC series (manufactured by Nissan Chemical Co., Ltd.) and MA-DGIC (above ( Ⅳ)), DA-MGIC (above (ⅵ)), TOIC (above (ⅲ)), etc. (manufactured by Shikoku Kasei).

The negative photosensitive resin composition of the present invention is (B) an epoxy resin having an epoxy equivalent of 500 g / eq. Or less with a benzene structure and two or more epoxy groups in one molecule, which contains a weight average molecular weight of 500 An epoxy resin having the above and / or softening point of 40 ° C. or higher (hereinafter, simply referred to as “(B) component”). Examples of the component (B) include long-chain bisphenol-type epoxy resins such as long-chain bisphenol A-type epoxy resins and long-chain bisphenol F-type epoxy resins, and phenols (phenols, alkyl groups) Substituted phenols, naphthols, alkyl-substituted naphthols, dihydroxybenzenes, dihydroxynaphthalenes, etc.) are reacted with formaldehyde in acidic catalysts to react with halogenated alcohols such as epichlorohydrin and methyl epichlorohydrin. The obtained phenolic epoxy resin, and the epoxy equivalent, weight average molecular weight, and softening point satisfy the aforementioned conditions. (B) The epoxy resin whose component is an epoxy equivalent, weight average molecular weight, and softening point which satisfy | fills the said conditions, as long as it is a polyfunctional epoxy resin which has a benzene ring, it is not limited to these. Specific examples of such (B) components include KM-N-LCL, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-4400H, EPPN-201, EPPN-501, EPPN -502, XD-1000, BREN-S, NER-7604, NER-7403, NER-1302, NER-7516, NC-3000H (all are trade names, manufactured by Nippon Kayaku Co., Ltd.) and epoxy resin 157S70 (commodity Name, manufactured by Mitsubishi Chemical Corporation).

Among these (B) components, the chemical resistance, plasma resistance, and transparency of the hardened material are high, and the hardened material has low moisture absorption. It is preferable that the epoxy resin (B -1), (B-2), (B-3), (B-4), (B-5), (B-6), (B-7), (B-8), and (B-9 ). More preferably, they are (B-1), (B-2), and (B-3), and more preferably, they are used by mixing (B-1), (B-2), and (B-3).

Among these preferred (B) components, the epoxy resin (B-5) is a reactant of a phenol derivative represented by the above formula (6) and epihalohydrin. As a general synthesis method of the epoxy resin (B-5), for example, it can be dissolved in a phenol derivative and epihalohydrin (epoxychloropropane and epibromopropane ( Epibromhydrin) and other mixed solvents are added with alkali such as sodium hydroxide. After the temperature is raised to the reaction temperature for addition reaction and cyclization reaction, the reaction solution is washed with water, separated and removed from the water layer, and finally distilled off from the oil layer Solvent method. It is well known that an epoxy resin (B-5) having a different main component can be obtained according to the use ratio of the phenol derivative represented by formula (6) and epihalohydrin used in the aforementioned synthetic reaction. For example, when an excessive amount of epihalohydrin is used with respect to the phenolic hydroxyl group of a phenol derivative, a trifunctional epoxy resin in which all three phenolic hydroxyl groups in formula (6) are epoxidized can be obtained as a main component. Of epoxy resin (B-5). With the reduction in the amount of epihalohydrin relative to the phenolic hydroxyl group, the phenolic hydroxyl group of a plurality of phenol derivatives is combined via the epihalohydrin, and the remaining phenolic hydroxyl group is epoxidized. The content increases. As a method for obtaining an epoxy resin (B-5) containing such a multi-polymer epoxy resin as a main component, in addition to a method for controlling the use ratio of the aforementioned phenol derivative and epihalohydrin, it can also be enumerated. A method for further reacting a phenol derivative with the obtained epoxy resin (B-5). The epoxy resin (B-5) obtained by this method is also included in the category of the epoxy resin (B-5) contained in the photosensitive resin of the present invention. The reaction between the phenol derivative represented by the formula (6) and epihalohydrin is usually carried out using epihalohydrin at a ratio of 0.3 to 30 moles, relative to 1 mol of the phenol derivative (equivalent to 3 mol of hydroxyl). It is preferably carried out using epihalohydrin in a ratio of 1 to 20 mol, more preferably in a ratio of 3 to 15 mol.

As the epoxy resin (B-5) contained in the resin composition of the present invention, any epoxy resin obtained by the reaction of a phenol derivative represented by the formula (6) and epihalohydrin can also be used. An epoxy resin (B-5), which is either an epoxy resin containing a phenol derivative as a main component or an epoxy resin containing a polymer of a phenol derivative. Since the epoxy resin (B-5) has good solvent solubility, low softening point and easy handling, it is preferable to use epoxy resin which is a monomer of phenol derivative and epoxy resin which is a dimer of phenol derivative. (An epoxy resin having a structure in which two phenol derivatives represented by formula (6) are bonded via epihalohydrin) or a trimer epoxy resin of phenol derivatives (having three phenols represented by formula (6) Any of epoxy resins (B-5) whose main component is a structure in which the derivative is combined with epihalohydrin. More preferably, it is an epoxy resin (B-5) which uses the epoxy resin of the monomer of a phenol derivative, or the epoxy resin of the dimer of a phenol derivative as a main component.

Hereinafter, the specific structure of the epoxy resin (B-5) of the phenol derivative monomer represented by Formula (6) is shown in Formula (6-1).

[Chemical Formula 14]

Hereinafter, the specific structure of the epoxy resin (B-5) which is a dimer of a phenol derivative represented by Formula (6) is shown by following Formula (6-2).

[Chemical Formula 15]

Hereinafter, the specific structure of the epoxy resin (B-5) of the trimer of the phenol derivative represented by Formula (6) is shown in the following Formula (6-3).

[Chemical Formula 16-1] [Chemical Formula 16-2]

In the present invention, for example, an epoxy resin represented by the formula (2) means an epoxy resin containing the epoxy resin represented by the formula (2) as a main component (the number of repeating units k is an average value). It also includes the case where the secondary components generated during the production of the epoxy resin and the high molecular weight body of the epoxy resin are included. The same applies to epoxy resins of formulae other than the quoted formula (2).

Specific examples of the epoxy resin (B-1) represented by the aforementioned formula (2) include KM-N-LCL (trade name, bisphenol A phenolic epoxy resin, manufactured by Nippon Kayaku Co., Ltd., Epoxy equivalent 195 ~ 210g / eq., Softening point 78 ~ 86 ° C), epoxy resin 157 (trade name, bisphenol A novolac epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 180 ~ 250g / eq. , Softening point 80 ~ 90 ℃), EPON SU-8 (trade name, bisphenol A phenolic epoxy resin, manufactured by Resolution Performance Products, epoxy equivalent 195 ~ 230g / eq., Softening point 80 ~ 90 ℃), etc. . Specific examples of the epoxy resin (B-2) represented by the formula (3) include NC-3000 series (trade name, biphenyl-phenolic phenolic epoxy resin, manufactured by Nippon Kayaku Co., Ltd.) , Epoxy equivalent 270 ~ 300g / eq., Softening point 55 ~ 75 ℃). A preferred example of the NC-3000 series is NC-3000H.

As specific examples of the epoxy resin (B-3) represented by the aforementioned formula (4), NER-7604 and NER-7403 (both are trade names and bisphenol F which is partly epoxidized) Type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 200 ~ 500g / eq., Softening point 55 ~ 75 ° C, NER-1302 and NER-7516 (both trade names and part of alcoholic hydroxyl groups are partially cyclized) Oxidized bisphenol A epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 200 ~ 500g / eq., Softening point 55 ~ 75 ° C), etc. Specific examples of the epoxy resin (B-4) represented by the aforementioned formula (5) include EOCN-1020 (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 190 to 210 g / eq., Softening Point 55 ~ 85 ℃). Specific examples of the epoxy resin (B-5) that is a reactant of the phenol derivative and epihalohydrin represented by the formula (6) include EOCN-6300 (trade name, manufactured by Nippon Kayaku Co., Ltd., Epoxy equivalent: 230 ~ 235g / eq., Softening point: 70 ~ 72 ℃). Examples of the epoxy resin (B-6) include polycarboxylic acid epoxy compounds whose production methods are described in Japanese Patent Laid-Open No. 2698499. The epoxy equivalent and softening point can be variously adjusted according to the type of the epoxy resin used as the raw material of the epoxy resin (B-6) and the introduction rate of the substituted group.

As a specific example of the epoxy resin (B-7) represented by the aforementioned formula (7), EPPN-201-L (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 180 ~ 200g / eq. , Softening point 65 ~ 78 ℃). Specific examples of the epoxy resin (B-8) represented by the aforementioned formula (8) include EPPN-501H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 162 to 172 g / eq., Softening) Point 51 ~ 57 ° C), EPPN-501HY (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 163 ~ 175g / eq., Softening point 57 ~ 63 ° C), EPPN-502H (trade name, Nippon Kayaku Co., Ltd. Manufactured by the company, epoxy equivalent 158 ~ 178g / eq., Softening point 60 ~ 72 ℃). Specific examples of the epoxy resin (B-9) represented by the aforementioned formula (9) include XD-1000 (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 245 to 260 g / eq.), Softened Point 68 ~ 78 ℃).

The epoxy equivalent of the (B) component contained in the negative photosensitive resin composition of the present invention is preferably 150 to 500, and more preferably 150 to 450. The weight-average molecular weight of the component (B) contained in the negative photosensitive resin composition of the present invention is preferably 500 to 15,000, and more preferably 500 to 9,000. The softening point of the component (B) contained in the negative photosensitive resin composition of the present invention is preferably 40 to 120 ° C, more preferably 40 to 110 ° C, 55 to 120 ° C, or 55 to 110 ° C. The epoxy equivalent in the present invention is a value measured by a method conforming to JIS K7236. The weight average molecular weight in the present invention is a value of a weight average molecular weight calculated by polystyrene conversion based on a measurement result of gel permeation chromatography. The softening point in the present invention is a value measured by a method conforming to JIS K7234.

The content of the component (A) in the negative photosensitive resin composition of the present invention is 1 to 50% by mass, preferably 2 to 30% by mass, and more preferably 3 to 20% by mass relative to the (B) component. . In another aspect, the content of the component (A) in the negative photosensitive resin composition of the present invention is preferably 1 to 30% by mass, 1 to 20% by mass, 2 to 50% by mass, 2 to 20% by mass, 3 to 50% by mass, or 3 to 30% by mass.

The negative-type photosensitive resin composition of the present invention contains (C) a photocationic polymerization initiator (hereinafter, simply referred to as "(C) component"). The (C) component contained in the photosensitive resin composition of the present invention is irradiated with radiation such as ultraviolet, far ultraviolet, KrF, and ArF excimer lasers, X-rays, and electron beams to generate cations, and the cations can become A compound of a polymerization initiator. Examples of the component (C) include aromatic sulfonium salts and aromatic sulfonium salts. Specific examples of the aromatic sulfonium salt include diphenylphosphonium tetrakis (pentafluorophenyl) borate, diphenylphosphonium hexafluorophosphate, diphenylphosphonium hexafluoroantimonate, and bis ( 4-nonylphenyl) phosphonium hexafluorophosphate, tolyl isopropylphenylphosphonium tetrakis (pentafluorophenyl) borate (manufactured by RHODIA, trade name: Rhodorsil PI2074), di (4-tributyl ) Ammonium tris (trifluorobenzylsulfonyl) methoxide (manufactured by BASF, trade name: CGI BBI-C1) and the like. Specific examples of the aromatic ammonium salt include 4-phenylthiodiphenylsulfonium hexafluoroantimonate (manufactured by San-Apro, trade name: CPI-101A), and phenylthiodiphenyl.鋶 Tris (pentafluoroethyl) trifluorophosphate (manufactured by San-Apro, trade name: CPI-210S), 4- ｛4- (2-chlorobenzidine), phenylthio, phenylbis (4- Fluorophenyl) hexafluoroantimonate (manufactured by ADEKA, trade name: SP-172), a mixture of 4-phenylthiodiphenyl hexafluoroantimonate, aromatic hexafluoroantimonate (ACETO Manufactured by Corporate USA, trade name: CPI-6976), and triphenylsulfonium tris (trifluorobenzylsulfonyl) methoxide (manufactured by BASF, trade name: CGI TPS-C1), tri [4- (4-ethyl Fluorenylphenyl) sulfonylphenyl] fluorene tris (trifluoromethylsulfonyl) methyl compound (manufactured by BASF, trade name: GSID 26-1), tris [4- (4-ethylfluorenylbenzene) Sulfonylphenyl]] tetrakis (2,3,4,5,6-pentafluorophenyl) borate (manufactured by BASF, trade name: irgacure PAG290), and the like. Among the components (C), in the photosensitive image forming step of the present invention, it is preferable that the aromatic chalcogenide salt has high vertical rectangular processability and high thermal stability. Among these, it is particularly preferred that it contains 4- ｛4- (2-chlorobenzidine) phenylthio, phenylbis (4-fluorophenyl), hexafluoroantimonate, and 4-phenylthio A mixture of aromatic hexafluoroantimonate of diphenyl sulfonium hexafluoroantimonate, tris [4- (4-ethylfluorenylphenyl) sulfonylphenyl] sulfonium tetra (2,3,4,5 , 6-pentafluorophenyl) borate.

The component (C) may be used alone or in combination of two or more in the negative photosensitive resin composition of the present invention. Since the component (C) has a function of absorbing light, when the component (C) is used in a large amount (for example, in an amount exceeding 15% by mass) in a thick film (for example, 50 μm or more), it is difficult to harden it when it is hardened. While light tends to sufficiently penetrate deep portions, on the other hand, a small amount (for example, an amount of less than 3% by mass) is difficult to obtain a sufficient curing rate when used. In the case of a thin film, sufficient performance is exhibited by adding a small amount (for example, 1% by mass or more) of the component (C). On the other hand, in the case of a thin film, when the component (C) is used in a large amount, although there is no problem regarding the deep part of light transmission, it is not economical to use an expensive starting agent in a required amount or more. From these points of view, the blending ratio of the (C) component in the photosensitive resin composition of the present invention is usually 0.1 to 10% by mass relative to the total mass of the (A) component and the (B) component, It is preferably 0.5 to 5% by mass. In another aspect, the blending ratio of the (C) component in the photosensitive resin composition of the present invention may be 0.1 to 5% by mass relative to the total mass of the (A) component and the (B) component. Or 0.5 to 10% by mass. However, in the case where the molar absorption coefficient of the component (C) at a wavelength of 300 to 380 nm is high, it is necessary to adjust the blending amount to an appropriate amount according to the film thickness when the photosensitive resin composition is used.

In the negative photosensitive resin composition of the present invention, in addition to the epoxy resin of the component (B), a (D) reactive epoxy monomer having a miscibility may be added in order to improve the pattern performance. As the reactive epoxy monomer of the component (D), an epoxypropyl ether compound that is liquid at room temperature can be used. Examples of the glycidyl ether compound include diethylene glycol diglycidyl ether, hexanediol diglycidyl ether, dimethylol propane diglycidyl ether, and polypropylene bicyclo Oxypropyl ether (manufactured by ADEKA, ED506), trimethylolpropane triglycidyl ether (manufactured by ADEKA, ED505), trimethylolpropane triglycidyl ether (low-chlorine type, Nagase ChemteX Corporation) Co., Ltd., EX321L), neopentaerythritol tetraglycidyl ether, dicyclopentadiene dimethanol diglycidyl ether (manufactured by ADEKA, EP4088L), etc. In addition, since these epoxy monomers generally have a high chlorine content, it is preferable to use a low-chlorine type that has undergone a low-chlorine manufacturing method or purification process. These can be used singly or in combination of two or more.

For the purpose of improving the reactivity of the resist and the physical properties of the cured film, a reactive epoxy monomer component is used. The reactive epoxy monomer component is mostly liquid. When the component is in a liquid state, if it is mixed by 20% by mass relative to the total amount of the photosensitive resin composition, it is easy to cause stickiness on the film after removing the solvent. Inappropriate conditions such as photomask sticking. From this point of view, when the monomer component is blended, its blending ratio is preferably 10 mass% or less (and higher than 0 mass%) relative to the total mass of the (A) component and the (B) component, It is particularly preferably 7% by mass.

In order to reduce the viscosity of the composition and improve the coating property, a solvent may be added to the negative photosensitive resin composition of the present invention. The solvent is an organic solvent generally used in inks, paints, and the like, and those that can dissolve each component of the photosensitive resin composition can be used without particular limitation. Specific examples of the solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, and cyclopentanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, ethylene glycol dimethyl ether, and dipropylene glycol di Glycol ethers such as methyl ether and dipropylene glycol diethyl ether, ethyl acetate, butyl acetate, butyl ruthoacetate, carbitol acetate, propylene glycol monomethyl ether acetate, and γ-butyrolactone , Alcohols such as methanol, ethanol, Saipansu and methylcellulose, aliphatic hydrocarbons such as octane and decane, petroleum ether, petroleum brain, hydrogenated petroleum brain, and petroleum petroleum solvents such as petroleum petroleum.

These solvents may be used alone or as a mixture of two or more. The solvent component is added for the purpose of adjusting the film thickness and coatability when applying the substrate. The amount of the solvent used to appropriately maintain the solubility of the main components, the volatility of the components, and the liquid viscosity of the composition is preferably 95% by mass or less in the negative photosensitive resin composition, and more preferably 10 to 90% by mass.

In order to improve the adhesion to the substrate composition, a miscible tackifier can be used for the negative photosensitive resin composition of the present invention. As the tackifier, a coupling agent such as a silane coupling agent or a titanium coupling agent can be used. Preferably, a silane coupling agent is mentioned.

Examples of the silane coupling agent include 3-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, trimethoxysilane, and vinyltri (2-methoxyethoxy). ) Silane, 3-Methacrylamidopropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycerylpropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-ureayltriethoxysilane, and the like. These tackifiers can be used alone or in combination of two or more. Since the tackifier does not react with the main component, it exists as a residual component after hardening in addition to the component acting on the interface of the substrate. Therefore, if a thickening agent is used in a large amount, physical properties may be deteriorated. In view of the fact that some substrates exhibit an effect even in a small amount, it is appropriate to use them in a range where no deterioration in physical properties occurs. The use ratio of the tackifier in the negative photosensitive resin composition is preferably 15% by mass or less, and more preferably 5% by mass or less.

For the negative photosensitive resin composition of the present invention, in order to further absorb ultraviolet rays and provide the absorbed light energy to a photocationic polymerization initiator, a sensitizer may be used. As the sensitizer, for example, thioxanthone, an onion compound (9,10-dialkoxyanthracene derivative) having an alkoxy group at the 9-position and the 10-position is preferred. Examples of the alkoxy group include alkoxy groups having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The 9,10-dialkoxyanthracene derivative may further have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group; and an alkyl sulfonate Group, carboxylic acid alkyl ester group, and the like. Examples of the alkyl group in the sulfonic acid alkyl ester group and the carboxylic acid alkyl ester group include alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, and propyl. The substitution position of these substituents is preferably the 2-position.

Specific examples of thioxanthone include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioranone, and 2,4-diisopropyl Thioxanthone and 2-isopropylthioxanthone. Preferred is 2,4-diethylthioxanthone (trade name: Kayacure (R) DETX-S, manufactured by Nippon Kayaku Co., Ltd.) or 2-isopropylthioxanthone.

Examples of the 9,10-dialkoxyanthracene derivative include, for example, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9 , 10-dibutoxyanthracene, 9,10-dimethoxy-2-ethylanthracene, 9,10-diethoxy-2-ethylanthracene, 9,10-dibutoxy-2- Ethyl anthracene, 9,10-dimethoxy-2-chloroanthracene, 9,10-dimethoxyanthracene-2-sulfonic acid methyl ester, 9,10-diethoxyanthracene-2-sulfonic acid methyl ester Esters, 9,10-dimethoxyanthracene-2-carboxylic acid methyl ester, and the like.

These sensitizers can be used alone or as a mixture of two or more. Most preferably, 2,4-diethylthioxanthone and 9,10-dimethoxy-2-ethylanthracene are used. The sensitizer component exhibits its effect in a small amount, so its use ratio is preferably 30% by mass or less, and more preferably 20% by mass or less for the component (C).

In the case of the negative photosensitive resin composition of the present invention, if it is necessary to reduce the adverse effects due to the ions derived from the component (C), trimethoxyaluminum, triethoxyaluminum, and triisopropoxyl can be added. Aluminum, alkoxy aluminum such as isopropoxy diethoxy aluminum and tributoxy aluminum, phenoxy aluminum such as triphenoxy aluminum and trimethylphenoxy aluminum, triethoxy aluminum, Aluminum stearate, aluminum tributyrate, aluminum tripropionate, aluminum triacetonate, aluminum tris (trifluoroacetonate), aluminum triethylacetonate, aluminum diethylacetonate dipivalamethane, and Plasma traps for organoaluminum compounds such as diisopropoxy (ethyl acetate) aluminum. The plasma trap can be used alone or in combination of two or more. The blending amount thereof may be 10% by mass or less with respect to the total solid content (all components except the solvent) of the negative photosensitive resin composition of the present invention.

To the negative photosensitive resin composition of the present invention, various additives such as a thermoplastic resin, a colorant, a thickener, an antifoaming agent, and a leveling agent may be further added as necessary. Examples of the thermoplastic resin include polyether fluorene, polystyrene, and polycarbonate. Examples of the colorant include phthalocyanine blue, phthalocyanine green, iodine green, crystal violet, titanium oxide, carbon black, and naphthalene black. Examples of the thickener include Auburn, Benton, and montmorillonite. Examples of the defoaming agent include, for example, silicone-based, fluorine-based, and polymer-based antifoaming agents. In the case of using such additives, the general standard for the amount of use thereof is, for example, 30% by mass or less in the photosensitive resin composition of the present invention. This amount can be appropriately increased or decreased according to the purpose of use.

To the negative photosensitive resin composition of the present invention, for example, barium sulfate, barium titanate, silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, alumina, and aluminum hydroxide may be added. , Mica powder and other inorganic fillers. The addition amount of the inorganic filler may be 60% by mass or less in the photosensitive composition of the present invention.

The negative photosensitive resin composition of the present invention is obtained by blending (A) component, (B) component, and (C) component with a solvent and various additives as necessary, and then mixing and stirring by a common method. Ready to prepare. Dispersers such as dissolvers, homogenizers, or triple roll mills can also be used for dispersion and mixing as needed. After mixing, filtration may be performed using a screen, a membrane filter, or the like.

The negative photosensitive resin composition of the present invention is preferably used in a state of a solution to which a solvent is added. When the negative-type photosensitive resin composition of the present invention dissolved in a solvent is used, for example, metal substrates such as silicon, aluminum, and copper; lithium tantalate; glass; ceramic substrates such as silicon oxide and silicon nitride; On a substrate such as amine, polyethylene terephthalate, etc., the negative photosensitive resin composition of the present invention can be applied using a spin coater to a thickness of 0.1 to 1000 μm. Next, under a heating condition of 60 to 130 ° C. for about 5 to 60 minutes, after removing the solvent to form a negative photosensitive resin composition, pre-baking is performed, and then a photomask having a predetermined pattern can be placed and irradiated with ultraviolet rays. Next, after performing heat treatment (post-exposure firing) at a temperature of 50 to 130 ° C for about 1 to 50 minutes, a developer solution can be used for the unexposed part. At room temperature to 50 ° C for about 1 to 180 minutes A development process is performed to form a pattern. Finally, a hardened product that satisfies various characteristics can be obtained by performing a heat treatment (hard roasting treatment) at a temperature of 130 to 230 ° C. These processing conditions are not limited and are a typical example. As the developing solution, for example, organic solvents such as γ-butyrolactone, triethylene glycol dimethyl ether, and propylene glycol monomethyl ether acetate, or a mixed solution of the foregoing organic solvent and water, or the like can be used. For development, a paddle type, spray type, or shower type developing device can be used. Ultrasonic irradiation can be performed as required. In addition, when the negative photosensitive resin composition of the present invention is used, aluminum may be mentioned as a preferable metal substrate.

The negative-type photosensitive resin composition of the present invention is coated on the base film using a roll coater, a die coater, a knife coater, a coating bar, a gravure coater, or the like. After that, it is dried in a drying oven set at 45 to 100 ° C. to remove a predetermined amount of solvent, and a cover film is laminated as necessary to form a dry film resist. At this time, the thickness of the resist on the base film can be adjusted to 2 to 10 μm. As the base film and the cover film, for example, films such as polyester, polypropylene, polyethylene, TAC, and polyimide are used. As these films, a film subjected to a release treatment with a silicone-based mold release treatment agent or a non-silica-based mold release treatment agent can be used as necessary. When this dry film resist is used, for example, the cover film is peeled off, and it is transferred to a substrate at a temperature of 40 to 100 ° C and a pressure of 0.05 to 2 MPa by a manual roller or a laminator, and dissolved in The negative photosensitive resin composition of the solvent may be subjected to exposure, post-exposure baking, development, and heat treatment in the same manner.

As described above, if the negative photosensitive resin composition is supplied as a dry film, the steps of applying and drying on the support can be omitted. This makes it possible to more easily form a cured product pattern using the negative photosensitive resin composition of the present invention.

When used as a MEMS package or a semiconductor package, it can be used by covering the MEMS or semiconductor element with the negative photosensitive resin composition of the present invention, or making a hollow structure for the MEMS or semiconductor element. As a substrate for MEMS and semiconductor packages, it is used on silicon wafers of various shapes. Metal films such as aluminum, gold, copper, chromium, and titanium are formed by sputtering or evaporation to a thickness of 10 to 5000 Å. A substrate or the like whose metal is micro-processed by an etching method or the like. In some cases, as an inorganic protective film, silicon oxide and silicon nitride may be formed with a film thickness of 10 to 10,000 Å. Next, a MEMS or semiconductor element is fabricated or provided on the substrate, and in order to block the element from the outside air, a covering or hollow structure needs to be fabricated. In the case of coating with the negative photosensitive resin composition of the present invention, it can be performed by the aforementioned method. In the case of producing a hollow structure, by forming a partition wall on the substrate by the method described above, and further patterning the dry film on the substrate by the method described above, it can be used as a laminate and a cover on the partition wall. Make hollow package structure. In addition, after manufacturing, if necessary, heat treatment is performed at 130 to 200 ° C. for 10 to 120 minutes, so that MEMS package parts and semiconductor package parts that satisfy various characteristics can be obtained.

In addition, the "package" is a packaging method or a product used to maintain the stability of a substrate, wiring, and components, and to block the intrusion of gases and liquids from the outside air. "Packaging" mentioned in this specification refers to a hollow package used to package an oscillator with a driver such as a MEMS and a SAW element, a surface protection to prevent deterioration of a semiconductor substrate, a printed wiring board, wiring, etc., and Resin packaging, etc. In addition, the so-called "wafer-level package" mentioned in this specification refers to a packaging method or a product thereof in which a protective film, terminals, wiring processing, and packaging are performed in a wafer state, and then cut into wafers.

The negative photosensitive resin composition of the present invention has a good image resolution and a high elastic modulus at high temperatures, and has been found to have a significant effect of good adhesion to various substrates other than silicon wafers. Therefore, the negative photosensitive resin composition is used in, for example, MEMS (microelectromechanical system) parts, micromechanical parts, microfluidic parts, μ-TAS (micro total analysis system) parts, inkjet printer parts, micro Reactor parts, conductive layers, LIGA parts, micro injection molding and stamping and stamping suitable for thermal embossing, spacers or stencils for micro printing applications, MEMS packaging parts, semiconductor packaging parts, BioMEMS and biophotonic components and printing Manufacturing of wiring boards, etc. Among them, it is especially used for MEMS package parts and semiconductor package parts.

In addition, as a product, a negative photosensitive resin composition (a mixture of a plurality of components) contained in the compound (A) has a triazacyclic ring compound, and the (B) component has a benzene structure and two or more rings The structural identification and content ratio analysis of each component of epoxy resin and (C) photocationic polymerization initiator can be measured by ¹ H-NMR, ¹³ C-NMR, LC-MS, etc., and Compare with the analysis results of the specimens. Moreover, if the structure of the epoxy resin of (B) component is clear, the epoxy equivalent, weight average molecular weight, and softening point can be obtained. [Example]

Hereinafter, the present invention will be described by way of examples. These embodiments are merely examples for better illustrating the present invention, and the scope of the present invention is not limited to the examples shown below.

Examples 1 to 4, Comparative Examples 1 and 2 (Preparation of Photosensitive Resin Composition) According to the blending amount (unit is parts by mass) described in Table 1, (A) a compound having a triazacyclo ring, (B) Epoxy resin, (C) Photocationic polymerization initiator and other ingredients, using a flask equipped with a stirrer, stirred and mixed at 60 ° C for two hours to obtain the present invention and a negative-type photosensitizer for comparison. Sexual resin composition.

(Coating, drying, exposing, and developing the photosensitive resin layer) Plasma CVD film formation on silicon (Si) wafer substrates and silicon nitride (SiN) at a thickness of 1000 上 on silicon wafers Then, each of the negative photosensitive resin compositions of Examples 1 to 4, Comparative Example 1, and Comparative Example 2 was coated with a spin coater to a film thickness (film thickness after drying) of 20 μm, and then a hot plate was used. Drying was performed at 120 ° C for 2 minutes, and each negative photosensitive resin composition layer was provided. For this substrate provided with a negative photosensitive resin composition layer, pre-baking was performed using a hot plate under the conditions of 65 ° C. for 5 minutes and 95 ° C. for 15 minutes, and an i-ray exposure device (photomask aligned exposure) Machine: made by USHIO Denki Co., Ltd.) pattern exposure (soft contact, i-line). After the exposed substrate was subjected to post-exposure baking (PEB) at 95 ° C for 6 minutes using a hot plate, propylene glycol monomethyl ether acetate was used for development at 23 ° C for 6 minutes according to the dipping method. A 200 ° C oven (under a nitrogen atmosphere) was subjected to a hard firing treatment for 60 minutes to obtain a pattern of a negative photosensitive resin composition hardened on a Si wafer substrate and a substrate after SiN was formed into a film.

(Sensitivity Evaluation of Negative Photosensitive Resin Composition) In the pattern exposure on the aforementioned silicon (Si) wafer substrate, the exposure amount with the best transfer accuracy of the photomask was taken as the optimal exposure amount, and each negative type was photosensitive. The sensitivity of the resin composition was evaluated. In this evaluation result, a composition having a smaller value of the optimal exposure amount means a higher sensitivity. The results are shown in Table 1 below.

(Resolution Evaluation of Negative Photosensitive Resin Composition) In the pattern exposure of the optimal exposure amount obtained based on the sensitivity evaluation of the aforementioned negative photosensitive resin composition, the line and space were 1: 1. Among the resist patterns analyzed without residue, the width of the finest pattern adhered to the substrate was measured to evaluate the resolution of the negative photosensitive resin composition. The results are shown in Table 1 below. Evaluation Criteria ○ (Good): The finest pattern width is 10 μm or less. × (defective): The finest pattern width exceeds 10 μm.

(Evaluation of adhesion of negative photosensitive resin composition to Si and SiN) Here, the adhesion is the shear strength (shear strength) when the pattern is peeled from the substrate by applying a force from the side surface of the pattern using a cutting tool. ). The higher this value is, the higher the adhesion between the substrate and the resin composition is, which is preferable. Specifically, a 100 μm × 100 μm (film thickness: 20 μm) block-shaped resist pattern was formed on each substrate with the optimum exposure obtained as described above, and an adhesion tester (manufactured by RHESCA) was used. The shearing tool measures the breaking load when a load is applied from a lateral direction to a position higher than 3 μm at a speed of 50 μm / sec. The results are shown in Table 1 below.

(Evaluation of the heat resistance of the negative photosensitive resin composition) A hardened product of the negative photosensitive resin composition was prepared with the optimal exposure amount obtained in the sensitivity evaluation of the negative photosensitive resin composition, and a DMA measuring device ( RSA-G2 (produced by TA Instruments), and the modulus of elasticity at 175 ° C was measured under conditions of a tensile mode, 1 Hz, and a ramp rate of 3 ° C / sec. The results are shown in Table 1 below.

[Table 1]

In addition, (A-1) to (G) in Table 1 are as follows. (A-1): trade name, TEPIC-VL, manufactured by Nissan Chemical Industries, Ltd., epoxy equivalent 135 g / eq. (A compound having a triazahexacyclic ring represented by formula (1), all of R ₁ are, R ₂ is an n-propenyl organic compound represented by the formula (1-1)) (A-2): trade name, TEPIC-UC, manufactured by Nissan Chemical Industries, Ltd., epoxy equivalent 195 g / eq. (With A triaza-hexacyclic compound represented by formula (1), _one of R ₁ is, an organic group represented by formula (1-1) is R ₂ is methylene, and the remaining two of R ₁ are, R ₅ It is a hydrogen atom-containing compound represented by the formula (1-4). (B-1): Trade name, KM-N-LCL, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 210g / eq., Softening point 85 ℃, weight average molecular weight 8000, average repeat number k = 4 (epoxy resin represented by formula (2)) (B-2): trade name, NC-3000H, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 285 g / eq., softening point 65 ℃, weight average molecular weight 700, average repeat number p = 2 (epoxy resin represented by formula (3)) (B-3): trade name, NER-7604, Nippon Kayakusho Company, epoxy equivalent 347g / eq., Softening point 71 ° C, weight average molecular weight 9000, average repeat number n = 4, m ≦ 1 (epoxy resin represented by formula (4)) (B-4): product Name, jER-1007, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 2000g / eq., Weight average molecular weight 2900 (C-1): photoacid generator (tri [4- (4-ethylfluorenylphenyl) sulfonium Phenyl] pyridine tetra (2,3,4,5,6-pentafluorophenyl) borate, trade name, PAG290 (made by BASF) (D-1): trade name, EX-321L, Nagase ChemteX strain Co., Ltd., epoxy equivalent 140g / eq. (Trimethylolpropane triglycidyl ether) (D-2): Trade name, EP-4088L, manufactured by ADEKA Corporation, epoxy equivalent 165g / eq. (Dicyclopentane Diene dimethanol diglycidyl ether) (E): Silane coupling agent (trade name, S-510, manufactured by Chisso Corporation) (F): leveling agent (trade name, Ftergengt222F, manufactured by Neos Corporation) ( G): Solvent (ethylene glycol dimethyl ether, trade name: HysolveMMM, manufactured by Toho Chemical Industry Co., Ltd.)

From the results in Table 1, it is clear that the elastic modulus at 175 ° C. of the negative photosensitive resin composition of the present invention (Examples 1 to 4) compared with the negative photosensitive resin composition of Comparative Examples 1 and 2. Higher, and the adhesion to Si and SiN is also high (at least equal).

(Adhesion Evaluation of Negative Photosensitive Resin Composition with LT and Al) The negative photosensitive resin compositions of Example 1 and Comparative Example 1 were evaluated by the same methods as the aforementioned sensitivity evaluation and the adhesion evaluation of Si and SiN. Adhesion of materials to LT (lithium tantalate) substrate and Al (aluminum) substrate. The results are shown in Table 2 below. The numerical unit in Table 2 is "MPa".

Table 2

From the results in Table 2, it is clear that the negative photosensitive resin composition (Example 1) of the present invention has higher adhesion to LT and Al than the negative photosensitive resin composition of Comparative Example 1.

(Production of Samples for Evaluation of Residues After Development) The residues after development referred to herein are residues of the negative-type photosensitive resin composition that must be removed by the development process and remain in the unexposed portion after development. Each PET film was coated with each of the negative photosensitive resin compositions of Example 1, Example 3, Example 4, Comparative Example 1 and Comparative Example 2 using a sprayer, and then heated at 120 ° C for 2 minutes using a hot plate. The solvent was dried under the conditions, and each negative photosensitive resin composition layer (dry film) having a thickness of 20 μm was provided. A sample for evaluation was obtained by attaching a PET film to each of the negative photosensitive resin composition layers obtained above in a laminator at 60 ° C and 0.3 MPa, at a temperature of 40 ° C. ℃ and humidity 90% RH for two weeks.

(Evaluation of Residues After Development) The negative photosensitive resin composition layer of the PET film was peeled off from the evaluation sample obtained above and exposed on one side under the conditions of 60 ° C. and 0.3 MPa, and was bonded to the After the silicon (Si) wafer substrate, a heat treatment was performed at 65 ° C for 5 minutes on a hot plate. Next, a silicon (Si) wafer substrate having a negative photosensitive resin composition layer obtained by peeling off the remaining PET film was subjected to a immersion method at 23 ° C. for 6 minutes using propylene glycol monomethyl ether acetate. Of development processing. The unexposed portion of the silicon (Si) wafer substrate after the development process was observed with a microscope (ECLIPS L150 manufactured by Nikon Corporation) at a magnification of 50 times. In the case where there is no residue, it is ○ (good) and in the case of residue. Is × (bad). The results are shown in Table 3 below.

table 3

From the results in Table 3, it is clear that the negative photosensitive resin composition (Example 1, Example 3, and Example 4) of the present invention is compared with the negative photosensitive resin composition of Comparative Example 1 and Comparative Example 2, The effect of suppressing the generation of residues after development is high. [Industrial availability]

Since the photosensitive resin composition of the present invention can form a pattern with high adhesion to various substrates, and has a high effect of suppressing the generation of residues after development, it is suitable for the fields of MEMS packaging parts and semiconductor packaging. In particular, in polymer capping such as SAW / BAW filters, the photosensitive resin composition of the present invention has both an elastic modulus at a high temperature and adhesion with various materials, so it is advantageous for molding. The formation of the cavity of the time can make the final product thinner, and the expansion of design freedom can be expected.

Claims (9)

A negative-type photosensitive resin composition comprising: (A) a compound having a triazahexacyclic ring represented by the following formula (1), In formula (1), R ₁ each independently represents an organic group, at least one of R ₁ represents an organic group having an epoxy group or an organic group having an oxetanyl group, and (B) has a benzene structure in one molecule And epoxy resins having an epoxy equivalent of 500 g / eq. Or less of two or more epoxy groups, and (C) a photocationic polymerization initiator, wherein (A) has a triazahexacyclo ring represented by formula (1) The content of the compound with respect to the (B) epoxy resin is 1 to 50% by mass, and the (B) epoxy resin satisfies at least one of the following conditions (i) and (ii): Condition (i): Weight If the average molecular weight is 500 or more, condition (i): the softening point is 40 ° C or more. The negative photosensitive resin composition according to item 1 of the scope of patent application, wherein at least one of R ₁ is an organic compound represented by the following formula (1-1), formula (1-2) or formula (1-3) base, In formula (1-1), R ₂ represents an alkylene group having 1 to 8 carbon atoms, In formula (1-2), R ₃ represents an alkylene group having 1 to 8 carbon atoms, R ₄ represents an alkyl group having 1 to 6 carbon atoms, . The negative photosensitive resin composition according to item 2 of the scope of the patent application, wherein any one of R ₁ is an organic group represented by the formula (1-1), an organic group represented by the formula (1-2), or An organic group represented by the formula (1-3). The negative photosensitive resin composition according to item 2 of the scope of patent application, wherein at least one of R ₁ is an organic group represented by the following formula (1-4), In the formula (1-4), R ₅ represents a hydrogen atom or a methyl group. The negative photosensitive resin composition according to any one of claims 1 to 4 in the scope of patent application, wherein (B) an epoxy equivalent of a benzene structure and two or more epoxy groups in one molecule It is 500 g / eq. The epoxy resin below is at least one selected from the group consisting of the following formula (2) to formula (9), and the epoxy resin (B-1) represented by formula (2): In formula (2), R each independently represents a glycidyl group or a hydrogen atom, at least two of a plurality of R are glycidyl groups, and k represents an average value, and is a real number in a range of 0 to 30; 3) Represented epoxy resin (B-2): In formula (3), R ₆ , R _7, and R ₈ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and p represents an average value, and is a real number in a range of 1 to 30; ) Represented epoxy resin (B-3): In formula (4), n and m represent average values, n is a real number in a range of 1 to 30, m is a real number in a range of 0.1 to 30, and R ₉ and R ₁₀ each independently represent a hydrogen atom and a carbon atom number as 1 to 4 alkyl or trifluoromethyl; epoxy resin (B-4) represented by formula (5): In formula (5), q represents the average value and is a real number in the range of 1 to 30; the reactant of the phenol derivative and epihalohydrin represented by formula (6) is epoxy resin (B-5): ; An epoxy resin obtained by reacting a polyprotic anhydride with a reactant of an epoxy compound having at least two epoxy groups in one molecule and a compound having at least one hydroxyl group and one carboxyl group in one molecule (B- 6); epoxy resin (B-7) represented by formula (7): In formula (7), s represents the average value, which is a real number in the range of 1 to 10; epoxy resin (B-8) represented by formula (8): In formula (8), t represents the average value, a real number in the range of 0.1 to 5; epoxy resin (B-9) represented by formula (9): In formula (9), r represents an average value, and is a real number in a range of 0.1 to 6. A dry film resist comprising the negative photosensitive resin composition according to any one of claims 1 to 5 in the scope of patent application. A cured product, which is a negative-type photosensitive resin composition as described in any one of claims 1 to 5 in the scope of patent application, or a dry film resist as described in the sixth scope of patent application Thing. A wafer level package comprising a hardened body as described in item 7 of the patent application. An adhesive layer between a substrate and an adherend includes a hardened object as described in item 7 of the scope of patent application.